Compounded oil



Patented Nov. 28, 1944 UNITED STATES PATENT OFFICE ooMPoU vnnn on.

Bruce B. Farrington and James 0. Clayton,

Berkeley, and Dorr H. Etzler, Albany, Calii., assignors to Standard Oil Company of California, San Francisco. Calif.. a corporation of Delaware No Drawing. Application September 15,1942, Serial No. 458,453

19 Claims. (01. 252-39) invention relates to the improvement of hydrocarbon oils and the like, in particular, mineral lubricating oils.

This application is a continuation-in-part ofour co-pending application Serial No. 322,946,

7 filed March 8, 19 40.

Hydrocarbon oils undergo deterioration during use or exposureto the atmosphere. Mere exposure to the air at relatively low temperatures,

as in the case of transformer oils and switchioils,

results in. the gradual formation of acidic oxidation products and the deposition of sludge. Use

,of a lubricating oil in the ordinary'gasoline engine, as in motor cars, results in a more rapid deterioration of the oil with deposition of sludge and the formation of varn-ish" on cylinder walls.

lubricating oils, transformer switch oils, and

the like.

Use of a lubricating oil in Diesel engines, which operate at higher temperatures and pressures than ordinary gasoline engines, results in even more rapid deterioration with resultant greater disadvantages. The temperatures and pressures involved in Diesel engine operation, around 400- 650 F. and 750-1200 pounds per square inch,

cause deposition from ordinary lubricating oils soap of butyric, capric, palmitic, stearic or oleic acid. Such soaps, among other things, reduce piston ring sticking in internal combustion engines, especially Diesel engines, apparently by loosening the cementitious deposits described above, or by inhibiting the formation of such deposits, or both. The action of the added soaps, by virtue of the analogy to the common cleansing or detergent action of soaps, came to beknown as a detergent" action and the soap additives came to be known as detergents."

The use ofthese soaps or detergents is not, however, without disadvantage. Among other things they are corrosive to certain alloy bearings, such as copper-lead and cadmium-silver alloy bearings, which are commonlyused in internal combustion engines. So destructive are certain of the soaps to these alloy bearings that they cannot be used satisfactorily in lubricatingoils for internal combustion engines.

It is an object achieved by the present inventionto Provide a valuable class of additives for It is a further object achieved by the present invention to improve the use of soap-like or metal alkyl carboxylateadditives in viscous hydrocarbon oils. I I

It is a stillfurther and a particular object achieved by the present invention to provide a class of soap-like or metal alkyl carboxylate'addiftives forlubricatin oils which are noncorrosive,

orsubstantially less corrosive than prior soap, additives, such as calcium stearate, toward alloy bearings.

Other objects achieved by the invention will be apparent from the description and the claims. We have discovered that substantial advantages result from incorporating in a-hydrocarbon oil or the like, especi g ll yg hydrocarbon lubricating oil, a polar substituted metal alkyl carboxylate wherein the polar substituent is of'a certain class and is in an alpha, beta or gamma position with respect to a metal alkyl carboxylate group.

The substituents that have been found to be desirable are those which contain a metal or metalloid and oxygen or sulfur; that is, we add to and use in hydrocarbon oils or the like alpha, beta or gamma substituted metal alkyl carboxylates, the alpha, beta or gamma substituent being a metalor metalloidand oxygenor sulfurcontaining radical. Preferably, those substituents are used wherein a metal, metalloid, o ygen or sulfur atom is directly bonded to the allqrl group of the metal alkyl carboxylate.

The additives of our invention may also be characterized by the following formulae:

1 v -d-cooM Jaime-occur l l I III , wherein M is a metal (or the hydrogen equivalent groups) by polar groups (including polar groups of the type represented by X, and/or other polar groups), etc.

It will'be apparent that three principal constitutional factors may be varied in the additives of this invention: (1) the nature and amount of the substituent X: (2) the nature of the alkyl carboxylic acid which is substituted and whose salt is formed; and (8) the nature of the metal M. These iaotors are discussed in more detail immediately below.

" (1) 'The mama x Substltuents comprising oxygen or sulfur or both and at least one of the following metals and metalloids are illustrative: sodium. potassium, magnesium, calcium, barium, zinc, cadmium,aluminum, silicon, lead, arsenic, antimony, bismuth, chromium, selenium, tellurium, iron, cobalt and nickel. The metallo-carboxy and metallo-thiocarboxy groups constitute an important class of substituents within the scope of the invention:

that is, the groups COOM, 008M, CSOM and CBSM, where M is the hydrogen equivalent oi a metal. Other typical examples of the substituent x are as follows:

In the above, M represents the hydrogen equivalent of a metal or metalloid, such as the metals and metalloids specifically enumerated above.

Those substituents are preferred which do not hydrolyze readily to produce corrosive acids. However, insofar as certain of the advantages of the metal alkyl carboxylates oi the invention are concerned, even those polar substituents which hydrolyze readily to produce corrosive acids are effective; for example,-as long as the hydrolyzable polargroup remains attached to the metal a j l carboxylate, it inhibits corrosion.

. (2). The alkyl carbomltcacid F For simplicity's sake, reference is made to the free, unsubstituted acids,and it is to be understood that in the practice of the invention a substituentwill be included and a ,metal salt formed, as indicated hereinabove. I

Monoand polybasic acids may be employed, and although open chain acids are preferred, cycl'oaliphatic acids and aliphatic acids havin an aromatic substituent in the alkyl chain (preferably removed by three or more carbon atomsirom the alkyl carboml group are comprehended by the invention. In all cases, however, the acid contains at least one carboxyl group attached toone alkyl or aliphatic carbon atom.

By the term alkyl carhoizylicv acid" is meant a carboxylic acid in which aCOOH group is attached to an aliphatic carbon atom, and by ascasia ing:

the term "metal alkyl carboxylate! is meant the metal salt of such an acid.

Illustrative of suitable acids are the follow Acids o] the acetic series, such as propionic. butyric, isobutyric, ,vgaleric, isovaleric, alphamethylbutyric, pivalic, caproic; alpha, alpha-dimethylbutyric; alpha, beta-dimethylbutyric, alpha-ethylbutyric; alpha-ethyl, alph'a-methylbutyric, capric, lauric, myristic, palmitic, stearic, etc.; also, unsaturated and/or hydroxy and other substituted members of the same series such as oleic, linoleic, iinolenie, licanic, lactic and ricinoleic acids. I

Acids of the oxalic acid series, such as malonie, succinic, isosuccinic, glutaric, adipic, eta; also, unsaturated dibasic acids, such as malls and fumaric; also, hydroxy dibasic acids, such as malic, mucic and tartaric.

Tribasic acids, such as citric and agaric acids.

Preference is given to those acids, generally the longer chain alkyl carboxylic acids, whose salts are oil soluble, although the lower acids, even acetic, when properly substituted and used in the form of appropriate metal salts, greatly improve the stability of hydrocarbon oils and inhibit ring sticking and associated phenomena. Cmand higher acids provide adequate oil solubility.

' (3) rue metal M Any monoor polyvalent metal capable of forming a sufllciently stable salt with the acid a chosen may be used. Metals which do not ex- 3' hibit adverse catalytic activity (such as promuting oxidation) and whose use does not result in'exeessive wear are preferred. Examples of metals whose salts may be formed and used in accordance with this invention are lithium, sodium, potassium, calcium, barium, strontium, beryllium, magnesium, aluminum, zinc, cadmlum, tin, lead, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, vanadium and bismuth; Basic and mixed, ,as well as normal simple salts may be employed. The metal of the COOM group and the metal of the X substituent may be the same, as in barium beta-phosphonato-isobutyrate cal-011000- HrP0r= 2 or the metal of the COOM group and the met or metalloid of the X substituent may differ', as in calcium alpha-borylbutyrate (cm-cm-cn-coo) F Ca 0 2 Examples 0'! substituted metal alkyl carboxylates contemplated by this invention are sodium, potassium, calcium, barium, aluminum, magnesium, zinc and nickel alpha, beta andgamma metallo- (e.- g. calcium, barium, or magnesium) phosphonato butyrates; the corresponding alpha, beta and gamma metallo-phosphonato valerat'es, caproates, caprates, laurates, myristates, palmitates, stearateaacrylates, crotonates, an- (gelates, oleates, lactates, malonates, succinates,

glutarates, adipates, maleates, fumarates, male ates, and citrates; also the corresponding-metallo-thiosulfato, silicato, metallo-carboxy, metallo-thiocarboxy, metallo-thiophosphonato, se-

leninyl, selenonyl and beryl substituted salts- (that is, the salts formed by substituting metallo-thiosulfato. silicato, etc. for metallo-phosphonatol.

- nates and glutarates.

Highly useful additives may be produced for use in accordance with the invention by introducing a long chain alkyl group into the molecule of an aliphatic polybasic' acid and forming a salt of the alkyl substituted polvbasic acid, which salt has at least two metallo-carboxyl groups. This may be accomplished in several ways; for example, as follows:

1. One carboxyl of a tribasic acid such as citric acid may be esteriiled to produce a di-acid ester of the acid and a long chain alcohol, andthe remaining unesterifled carboxyls are saponifled.

2. A long chain alkyl group is substituted in a It will be apparent to one skilled in the art that all of the possible substituents X cannot be introduced into each of the positions alpha, beta and gamma of every alkyl carboxylic acid. Thus the presence in analkyl carboxylic acid of an alpha, beta or gamma substituent, for example an hydroxyl substituent, may hinder the further substitution of the alpha, beta or gamma posi- X within the scope of the invention, or adifier- -ent position in the .alkyl carboxylic acid, or a different alkyl carboxylic acid may be chosen for substitution; or the hindering alpha, beta or gamma group, such as an hydroxyl group, may be replaced by the desired substituent.

Various methods of forming the metal salts may be employed, one such method being to form an alkali metal salt (as by neutralizingthe acid, or saponifying the corresponding ester, with an alkali metal hydroxide) and using the alkali metal salt per se or converting it into a polyvalent metal salt by adding to an aqueous solution of the alkali metal salt, a water soluble salt of a polyvalent metal, thus producing double decomposition and precipitation of the polyvalent metal salt.

The substituted metal alkyl carboxylates of this invention improv'e'hydrocarbon oils in several respects. One of the most important imboxylates in mineral oil lubricants is their marked detergent eil'ect, unaccompanied by corrosion oraccompanied by relatively little corrosion of hard alloy bearings. This contrasts with excessive corrosion of similar bearings when prior art soaps, such as calcium stearate and calcium naphthenate, are used. Also, used oil inspections (such as increase in viscosity, increase in neutralization number, and increase in naphtha insoluble matter in the used oil) are benefited by the presence of small amounts of the substituted metal alkyl carboxylates of the invention, or at least are not as adversely affected as the commoner soaps and unsubstituted metal alkyl carbo'xylates. Moreover, the metal alkyl carbonylates of the invention render oils more stable toward oxidation than the base oils.

The following specific examples will show how a .number of properties of hydrocarbon oils are benefited by, and will provide a comparison for judging the relative utility of, the substituted metal alkyl carboxylates of the invention.

- Emmet: I i A base 011 (an SAE blend of 10% Western acid treated naphthenic base 011 and 30% Westem parafllnic base oil) was tested, with and without the presence of metal alkyl carboxylate additives, to determine its corrosiveness to various alloys of the type used in bearings of internal com.- bustion engines. The Strip Corrosion Test was employed in these determinations, this test being as follows:

.Thin sheets of the indicated bearing metals were cut into strips (copper-lead, 1'5" x 1%" x.

.' P cadmium-silver, /z".x 1%" x and 1 tion by a certainsubstituent X of the present "invention. In such case, a difierent substituent these strips were immersed in the exemplified oils carried in 2" x 20" glass test tubes; these test tubes were carried in an oil bath maintained at 300 1 .11" F. Each test tube contained approximately 300 cc. of oil, and air was bubbled through each tube at the rate of 10 liters per hour. .At the end of each of three 24-hour periods, the strips were removed from the oils, washed with petroleum ether and carefully wiped with a soft cotton cloth; weight losses of the strips were measured in connection with the weight of each individual strip. The duration of the tests was 72 hours, and the weight losses tabulatedbelow are those found at the end of each 24-hour period.

The increase in viscosity of the oil, the neutralization number of the oil at the conclusion of each test, and the amount of naphtha insol- -ube matter at the conclusion of each test,.were

also measured. The results of the tests are set forth in Table I below, the additives referred to having been used in the amount of 0.5% by provements resulting from the use of these carweight based on th oil:

-' 1 Table I Fresh 011 m 011 ell-Pb strip Cd-AI viscosity vicosity Neutral- 5 3 011 Additive ization "01m number mes 241m. 431m. 72hrs. 24hrs. 431m. 121m. 100r.210r.1001 .2101-*. Western None -4 0.3 1.5 5.5 0.0 0.0 .0 032 31.0 1041 000 200 100 SAE 30 blend.

D0 01 but ate 3.0 13.3 31.4 0.0 15.3 43.0 028 51.1 Do on 201. ylbutyrateas 44.0 111.0 0.0 11.0 41.1 032 51.0 1442 100 401 100 D0.--" CB 18111'8t6 14.2 67.2 97.9 12.4 16.3 15.7 630 57-3 1148 -1 4.49 143 Do Us 18111110115"-.. 41.3 123.0 1004 0.3 33.2 00.2 032 51.0 1301 15.3 3.01v 221 Do 0381011110 844 152.5 20111 0.0 34.3 02.0 053 51.3 1340 13.0 p 4.02: 243 p0 Ba bteeta-phosphonatoisobuty- +0.4 +0.8 +0.3 0.1 0.2 0.3 034 00.0 844 02.4 0.44 20 PB 4 Do---" Ba thiosulfatoacetatc 0.0 0.1 0.3 00 0.0 0.0 030 31.0 341 02.0 1. 05 1 14 Do Us silicatotetraacetate 1.4 1.0 1.4 +0.2 +0.2 40.4 031 51.0 1213 12.1 4.05 21s Exmruli Oil was placed in a beaker in contact with air.

- maintained at a given temperature, and protected against drafts until darkening due to pxidation had occurred. A sample of the original oil was placed in a glass cell 50 mm. square by 7 mm. thick, and an equal sample of the exposed oil was placed in a second similar glass cell. The glass cells were placed equidistant from an electrlc light. The light that passed through each glass cell was caused to impinge on a photoelectric cell. The two photoelectric cells were mounted in two arms of a Wheatstone'bridge. The difference in light transmissions, caused by the diflerent colors of the 'oils, was thusresistered on the Wheatstone bridge. The readings of the bridge were calibrated against the standard ASTM color numbers, and from this the readings of the bridge could be converted into ABTM color numbers (Method D155-34T).

A base oil (Western paraihnic SAE 30) and the same base oil plus 0.5% 'by weight of in-' hibitor were tested, substituted metal alkyl car-- boxylates being used as the inhibitor. The results are set forth in Table II below:

' The base oil employed was a Western SAE 30 blend (70% Western acid treated naphthenic' and 30% Western parafilnic), The additives aseasia nc(on)--coo /Ca 12.. (om-coo Calcium alpha-elcosyl-tartrate In the formulae, R1 represents the normal cetyl (CzsHsa) group, R2 represents an alkyl group con taining, on the average,- l2 carbon atoms, R: represents an alkyl group containing, on the average, 18 carbon atoms, and R4 represents the scribed in Industrial and Engineering Chemistry,

vol. 28, page 26 (1936) was used. A temperature'of 340 F. was used and the results are'reo ported in cubic centimeters of oxygen absorbed per 100 grams of oil.

Corrosion.The Strip corrosion test of Example 1 was employed.

Engine test-A single cylinder Lauson gasoline 85 spark-ignition engine, 2% inch bore and 2 /2 inch stroke; loaded with an induction generator, was

operated under extremely severe conditions, de-

were calcium alpha-cetylmalonate, calcium al-- pha-tetradecenyl succinate, calcium-'alpha-eicosenylsuccinate, and calcium alpha-eicosyltartrate, these additives having the following structural formulae:

' r c o o Ri('JH Ca v Calcium alpha-oetyl-malonate Calcium alpha-eioosenyl-succinate signed to develop fully the tendency of the crankcase lubricant to deteriorate with gum formation and piston ring sticking: operation was at 1600 revolutions per minute; engine jacket temperature was maintained at 375 'F.; crankcase oil temperature was maintained at 220 F.; at periods .of 15 hours the operations-were interrupted and the condition of the piston rings determined.

Wear.The Weeks wear testing machine was used. In the operation of this machine a /2 inch steel ball is pressed against a 1% inch steel cylinder which is' rotated at 600 revolutions per minute and which dips intothe oil being tested. The test lasts 16 hours and the body of the oil is held at 300 F. The results are reported in inches of wear 10 as measured on the cylinder.

Film strength-The film strength was measured by the use of the Timken'machine as described inthe S. A. E. Journal, vol. 28, page 53 (1928), and the results are reported in pounds pressure at failure. 1

During some of theabove tests certain other properties were measured, such as viscosity, neutralization number, etc., and the measurements are recorded along with the results of the principal tests. 7 I

The various test results, are recorded in Tables III and IV below. The calcium alpha-cetylmalonate and calcium alpha-eicosenylsuccinate were used in all the tests in the amounts of 0.5% and 0.34%, respectively, by weight based on the oil. In some tests the calcium alpha-tetradecenyl succinate was used in the amount of 0.5% by weight based on the oil, but in others it was used in lesser amounts as indicated in parentheses in the tables below.

Table III Strip corrosion st gi figy oxygen Inspection at 72 hours a Base oil Additive (AS TM g ggg, Pb Cd Ag mp Viscosity co or in 2 hrs.) increase (SUV) in ase Neutral- Nophtha izatigg insotlrella lo 24 48 72 2 48 72 um i ms I hrs. hrs. hrs. hrs. hrs. hrs.

Western Nil -Q. 6 200 0.7 4.7 13.9 0.1 0.2 0.4 477 11.6 2.80 EIA (I; 3 0 v o 0.5% teCn alpha-,cetyl-mal- 95 0.9 6. 0 9- 8 0- 2 0.4 0.3 no 7.0 1. 21 29 one D0 0.5% 03: alpha-tetra-decenyll- (0. 18%) 30(0. 18%) 0. 8 1. 1 1. 1 0. 2 0. 4 O. 3 216 6. 7 1. 33 16 so a e. D0 0.34% er alphs-eicosonyl- K 50 0. 6 l. 1 1.8 0.0 0. 1 0. 1 197 6. 6 0. 68 16 succ a D0 0.23%(33 alphs-eicosyl-tsr- 1- 105 3.8 4.9 5.0 1.0 1.2 0.0 290 9.4 1.20 62 Table IV Engnm test m gg Trtnkentfllm wearXlD' in Base on Additive Hours to cause Relative ring 16 hours at 235 ring sticking slot cleanliness 300' r.

1 80 Poor 288 120 0.5 Ca a1 ha-cetyl-m nlnnnfe 75 B11 143 160 0.552 Ce alfiha-tetrsflecenylsuccinate 0 1 1 1630.27 120(0. 2%) 0.34% Ga alpha-eioosenyl-succlnate- 120+ Good 106 220 1 0.63% On alphs-cicosyltsrtrato 60+ Foir+ The substituted metal alkvl carboxylates of the invention may be advantageously added to any hydrocarbon oil or lubricating oil, such as the more viscous distillates and residues from petroleum oil, viscous olefin polymers, and viscous oils derived from oxides of carbon or other forms of carbon by hydrogenation, and they may be added with advantage to any of the newer synthetic lubricants, such as amyl naphthalene. The additives of our invention may be used in viscous hydrocarbon oils ranging in viscosity from about 60 SSU or lower at 100 F. to 160 SSU or higher at 210 F. The metal alkyl carboxylates may be used, in the finished oil, in amounts ranging from 0.1% or less to 10% or more by weight based on the finished oil, but preferably it is used inamounts of about 0.1 to usually 0.5 to 2%. Concentrates may be prepared containing more than and up to 50% ormore of the metal alkyl carboxylate of the invention, alone or together with another additive or other additives,

and the concentrate may be diluted with more wear, and film strength agents, etc. Specifically.

the additives of this invention maybe used in mineral or hydrocarbon oils in combination with any one or more of the following:

(4) Carboxylate esters having an alkyl hydroxy substituent (an hydroxy substituent attached to-an alkyl carbon atom) near a carbonyl roup of the ester. such as the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl,

lauryl, dodecyl, tetradecyl, cetyl and octadecyl esters of alpha, beta or gamma hydroxy propionic acid, and the corresponding esters of alpha, beta or gamma hydroxy butyric, valeric, caproio, enanthic, caprylic, capric, lauric,- myristic, palmitic, stearic, and arachidic acids, as well as the corresponding esters of tartonic, tartaric and citric acids.

(1) Unsubstituted or corrosive carboxylate salts such as the calcium, barium and aluminum The structural formulae and preparation of typical additives capable of use in accordance with this invention are given below:

Barium thiosulfatoacetate .19 mm chloro acetic acid are dissolved in 1 cc. of water and the solution is neutralized with a saturated solution of 10.6 grams of sodium carbonate. 50.3 grams or sodium thiosulfate pentahydrate are added to the neutralized solu- "tion and the solution is evaporated to about onehalf of its original volume. The barium salt is then precipitated by adding barium chloride and is filtered oil and dried.

Calcium silicatotetraacetate The structural formula-of this substanceis as follows:

(SiOKCHaCOO) 4) Ca:

Barium beta-phosphonato isobutyra The structuralformula of this substance is as follows: i

CH|--CH-COO Hr-POF 2B v 500 grams of PC]: are mixed in a 2 liter flask with 800 cc. of dry alcohol-free acetone. 80 grams of aluminum chloride are added in small portions. After the rapid evolution of l-ICl has subsided the ilask is heated on a water bath to remove additional HCl. Diacetone phosphorus chloride is thus formed. It is hydrolyzed by adding'it to water. The resulting impure diacetone phosphinlc acid is recovered by evaporating of! the water. It is purified by dissolving it in alcoalcohol; dissolved in water and filtered. The acid is obtained by acidification with HCl followed by evaporation. The solid residue is extracted with alcohol, filtered and evaporated to dryness. The purified diacetone 'phosphonic acid is oxidized with nitric acid and then with fuming nitric acid. The excess fuming nitric acid is removed by heating on a water bath. The impure beta-phosphonato butyric acid is dissolved in water and barium hydroxide is added until it is strongly alkaline. This solution is heated, to'boiling and.

filtered. The filtrate is discarded since the barium salt of thedesired acid is only slightly soluble in hot water, while impurities dissolve. The

' residue remaining on the filter is extracted with cold water and the extract is evaporated to d yness.

Calcium alpha-cetulmalonate The structural formula of this substance is given in Example 3 above.

Sodium ethylate is produced by treating 100 cc. of absolute alcohol with 12 grams of .sodium.

Sodium diethyl malonate is then precipitated by adding 80 grains of diethyl malonate I to the sodium ethylate. Dlethyl alpha-cetylmalonate' is then formed by adding 190 grams of cetyl iodide washed, dried, and extracted with ethyl ether to remove excess cetyl iodide. The desired calproduction of flns is mixed in i101 and precipitating the ammonium salt with 1 ammonia. This ammonium salt is washed with talned above.

white, curdy precipitate which is washed free 0! to the above sodium diethyl malonate and hesit ing the mixture at 212 F.. Sodium iodide is removed by washing with water. Potassium alpha-cetylmalonate is then made ,by hydrolyzing -the diethyl alpha-cetylmalonate with 520, cc. of a 10% KOH solution employing a temperature of 212 F. for 24'hours. salt is salted out from the aqueous solution,

The potassium cium alpha-cetylmalonate is then prepared by suspending grams of potassium salt in a 50-50 alcohol-water mixture, heating the mixture to 190 F. and adding excess calcium chloride solution. The precipitate is washed and dried, yielding the desided calcium alpha-cetylmalonate.

Calcium alpha-tetradecer ulsuccinate The structural iormula of this substance is given in Example 3 above.

An olefinic polymer of average chain length C11 produced as a high boiling residue in the gasoline by polymerization of ole- 25% excess over molecular proportion with maleic anhydride and the mixture is heated in an iron pressure vessel, without agltation, at 400-450 F. for 4 to 8 hours. The pressure developed does not exceed pounds per square inch. The product, tetradecenylsuccinic anhydride, is distilled under vacuum to remove unreacted polymers and maleic anhydride. A neutralization number of the tetradecenyl succinic anhydride is then taken to determine the amount of water theoretically required for hydration. The theoretical amount of water is added and the anhydride is digested under reflux for 1 hour at 195 F.. thus forming tetradecenylsuc-" cinic acid. A neutralization number of the acid is taken to determine the amount of potassium hydroxide required for making the potassium salt. The tetradecenylsuccinic acid is neutralized by heating at 180 F. for 30 minutes with a slight excess of potassium hydroxide in 25% aqueous solution. {The desired calcium alpha tetradecenylsuccinate is prepared by adding an equivalent amount of calcium chloride in 10%- solution to the solution of potassium salt as ob- The product is obtained as a impurities.

Calcium alpha-eicosenvlszwcinate The structural formula of this substance is also given in Example 3 above. It is prepared in exactly the same manner as calcium alphatetradecenylsuccinate except that a Can olefin polymer is used in place of the C14 oleiln polymer.

We claim: 1 v

1. A composition of matter,-comprising a major proportion of a hydrocarbon oil and a small amount, not less than about .1% by weight based on finished oil, of a metal alkyl carboxylate, substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylat'e group by a substituent containing at least one element of the group consisting of metals and metalloids and at least one element of the group consisting of oxygen and sulfur.

2. A composition of matter, comprising a I major proportion of an oil of lubricating viscosity and a small amount, not less than about 0.1%; by weight based on finished oil, of a metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing at least one element selected from the group consisting of metals and metalloids and at least'one element from the group consisting of oxygen and sulfur, said substituent being. at-

tached to said allwl carbon atom through one of said elements.

' mlyvalent metal is an 2,303,512 1 a. The composition r claim 2, wherein said substituent contains a metal and oxygen. 7

4. The composition of claim 2, wherein said Q substituent contains a metal and sulfur.

metal alkyl carboxylate substituted on an "alpha,

beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing a metal, oxygen and phosphorus' 8. A composition of matter, comprising a major proportion of a hydrocarbon oil of lubricating viscosity and a small amount, suflicient to improve the oil, of an oil-soluble polyvalent beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing a metal, sulfur and phosphorus.

9. A composition of matter, comprising a major proportion of a hydrocarbon oil of lubricating viscosity and a small cating viscosity and a small amount. sufllcient to based on the lubricant of a polyvalent metal salt 1 metal alkyl carboxylate substituted on an alpha amount, sumcient to improve the oil. of an oil-soluble polyvalent metal Y alkyl carboxylate substituted on an alpha, beta a major proportion of a hydrocarbon improve the. oil, of an oil-soluble polyvalent metal alkyl carboxylate substituted .on' an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent, containing boron and oxygen.

11. A petroleum lubricating oil containing about 0.1 to 5%. by weight based on finished oil of a polyvalent metal alkyl 'carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing at least one element selected from the group consisting of metals and metalloids and at least one element selected from the group of oxygen and 12. The composition of claim 11, wherein said earth metal.

13. A composition of matter, comprlsinga con atom by asubstltfrom the group consisting of metals and metal- .loids and at least one element selected from the group consisting of oxygen and sulfur.

14. A lubricant comprising a mineral oil of lubricating viscosity and about 0.1 to 5% by weight based on the lubricant of a polyvalent metal salt of an aliphatic carboxylic acid substituted on an aliphatic carbon atom alpha, beta or gammato a metal alkyl carboxylate group by a metallo mereapto group.

15. A lubricant comprising a mineral oil of lubricating viscosity and about 0.1 to 5% by weight based on the lubricant of a polyvalent metal salt of an aliphatic carboxylic acid substituted on an aliphatic carbon atom alpha, beta or gamma to a metal alkyl carboxylate group by a metallo phosphonato group. Y

16. A'lubricant comprising a mineral oil of lubricating viscosity and about 0.1 to 5% by weight of an aliphatic oarboxylic acid substituted on an aliphatic carbon atom alpha, beta or gamma to a metal alkyl carboxylate group by a'metallothiophosphonato group.

17. A petroleum lubricating oil comprising aboutv 0.1 to 5 per cent by, weight based on finished oil' of'a polyvalent metal salt of a fatty acid containing not less than :ten carbon atoms and substituted'on an alpha, beta or gamma carbon atom with respectto the metal darboxylate group by a substituent containing at least one element selected from the group consisting of metals and metalloids and atleast one element selected from the group consisting 'of oxygen and sulfur, s'aid substituent being attached to said alkyl carbon atom through one of said'elemen 18. A petroleum lubricating .oil comprising a small amount each of a metal salt of a phenol and a metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom by a substituent containing at least one element selected from the group consisting of metals and of phenol and said metal alkyl carboxylate are polyvalent metal salts.

' BRUCE B. FARRINGTON.

JAMES .0. CLAYTON. DORR H. E'I'ZLER,

oil-soluble,

uent containing atleast one element selected- 

